American Chemical Society
cg060762r_si_001.cif (15.89 kB)

4,4‘-Dipyridyl-N,N‘-dioxide Complexes of Metal-Thiocyanate/Selenocyanate:  π-Stacked Molecular Rods as Three-Dimensional Support for Two-Dimensional Polymeric Sheets and Intra/Interchain S···S Interaction Dependent Architecture of the (8) Synthon Driven Assembly of One-Dimensional Polymeric Chains

Download (15.89 kB)
posted on 2007-07-03, 00:00 authored by Atish Dipankar Jana, Subal Chandra Manna, Georgina M. Rosair, Michael G. B. Drew, Golam Mostafa, Nirmalendu Ray Chaudhuri
Three supramolecular complexes of Co(II) using SCN-/SeCN- in combination with 4,4‘-dipyridyl-N,N‘-dioxide (dpyo), i.e., {[Co(SCN)2(dpyo)2]·(dpyo)}n (1), {[Co(SCN)2(dpyo)(H2O)2]·(H2O)}n (2), {[Co(SeCN)2(dpyo)(H2O)2]·(H2O)}n (3), have been synthesized and characterized by single-crystal X-ray analysis. Complex 1 is a rare example of a dpyo bridged two-dimensional (2D) coordination polymer, and π-stacked dpyo supramolecular rods are generated by the lattice dpyo, passing through the rhombic grid of stacked layers, resulting in a three-dimensional (3D) superstructure. Complexes 2 and 3 are isomorphous one-dimensional (1D) coordination polymers [-Co-dpyo-Co-] that undergo self-assembly leading to a bilayer architecture derived through an (8) H-bonding synthon between coordinated water and dpyo oxygen. A reinvestigation of coordination polymers [Mn(SCN)2(dpyo)(H2O)(MeOH)]n (4) and {[Fe(SCN)2(dpyo)(H2O)2]·(H2O)}n (5) reported recently by our group [Manna et al. Indian J. Chem. 2006, 45A, 1813] reveals brick wall topology rather than bilayer architecture is due to the decisive role of S···S/Se···Se interactions in determining the helical nature in 4 and 5 as compared to zigzag polymeric chains in 2 and 3, although the same (8) synthon is responsible for supramolecular assembly in these complexes.